Adsorbed intermediates of formaldehyde oxidation and their role in the reaction mechanism.

Formaldehyde oxidation was studied on the basal planes of platinum single crystals. Electrochemical and IR spectroscopy data give new information on the mechanism of oxidation. Formaldehyde oxidation at platinum electrodes is a surface-sensitive reaction. From the three basal planes of Pt(hkl), Pt(111) is the most active one. The less active surfaces Pt(100) and Pt(110) are blocked by adsorbed carbon monoxide at the initial stages of the reaction as the formaldehyde is admitted in the solution with the electrode polarized at 0.05 V. Besides CO(ad), other adsorbed species are formed. From these, methylene glycolate, H2COO(ad), is the intermediate of the fast oxidation pathways forming CO2 and HCOOH as soluble products. According to IR data the yields of soluble products at Pt(111) were calculated at 0.6 V, giving 63% for HCOOH and 37% for CO2. At 0.05 V the Pt(111) surface becomes slowly blocked by CO(ad), as observed when the electrode was left in contact with the formaldehyde solution over a period of several minutes. The same blockage occurs during a cyclic voltammogram, which causes a lowering of activity during the second potential scan. A general scheme of the reaction is proposed.